Treatment of hydrocarbons



Patented June 16, I942 siren STATE s1 PATENT OFFICE. v

TREATMENT OF HYDROCARBONS' Gustav Eglofi and Charles G. Dryer, Chicago, 111.,

assignors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Original Serial No. 216,068.

application June 21, 1938, Divided and this application November 12, 1940, Serial No. 365,230

. 8 Claims.

carbon distillates containing appreciable quantities of oleflnic and other unsaturated hydrocarbons are subject. The art of using inhibitors in unstable cracked gasolines is now one of comparatively long standing and a large number of individual compounds'and classes of compounds have been developed for practical use, all of which apparently possess the characteristic of being more or less readily oxidizable so that the peroxidic compounds which are primarily formed when ole-containing gasoiines are in contact with air or other oxidizing gas mixtures are decomposed and the sequence of the chain reactions leading tothe formation of higher boiling polymers and resinous products which cause the de-' terioration .of the gasoline in respect to color, gum content, and antiknock value is stopped for a time depending upon the 'e' fliciency or the in-v hibitor, the degree of unsaturation of the oil and the extent of its exposure.

It isrecognized that the inhibitor art is known to include the use of such compounds as phenols, amines, and aminophenols and crude primary Q products containing these compounds, and no basic claim is made therein to the broad use of any of theseclasses. The present invention is specially concerned. with alimited group of compounds which have n found to possess good inhibiting potency combined with resistance to accidental removal by contact with water or caustic soda which occurs at many points in the storage systems of oil refineries.

In one specific embodiment the present invention comprises the treatment of unstable gasolines particularly cracked gasolines to materially arrest the deterioration thereof byadding to said ,gasolin'es relatively small percentages of disubstituted aminophenols, in which one of the amino hydrogen atoms has been replaced by an alkyl group and the other being a hydroxy alkyl group.

Compounds of the above type, inaddition to specially with the having high inhibiting emciency, have been found to have considerable resistance to removal by accidental' water or aqueous alkali contacts which gasolines containing them encounter under normalrconditions of service in oil refineries; Typical data showing the results obtained in practice with these compounds-will be given in a later section.

The following example is given to illustrate the general methods of preparing compounds of the present character: I

i N-n-butylvN-b-hydrozy ethyl p aminophenol The tabulation given below shows the mixture of compounds which were reacted to form the desired compound:

, Parts by b-Hydroxy-ethyl p-aminophenol n-Butyl bromide"; 27.4 Sodium bicarbonate 16.8 Ethyl alcohol r 200.0

The above mixture of compounds was refluxed for about 12 hours and the contents were then poured into an excess of water after which the water-oil mixture was extracted with ether. The combined ether extracts were heated weight 30.6

to distill oil the ether and then subjected to further distillation at a pressure of 4 mm. absolute. A yield of 28.1 parts by weight of the desired com pound boiling at 183186 C. under the reduced pressure was obtained which amounted to 81% of the theoretical yield. A redistiila'tion of this material showed a boiling range of 182-483 C. at the same reduced pressure. The principal restructural equation:

b-Hydroxy-ethyl N-n-butyl-N-b-h am p-sminophenol other p-amlnop The present "class of compounds is suflici'en potent so that only minorquantities are neces- The following table is introduced to shdw thev character of the results obtainable in practice by the use of the present type of inhibitors although 55 not with the intent oi unduly limiting the invenot the yessel action taking place is given by the following a standard inhibitor.

adding to the gasoline a relatively small amount tions proper scope. In all cases 0.01% of the 4. A method for stab" gasoline against deterioration thereof'on storage which comprises.

inhibitor by weight of the gasoline was used.

the higher molecular weight mixed substituted compounds there is a very low percentage removal by water washing although they are considerably affected by the action of'caustic soda.

The effective inhibitor ratio used in the table indicates the relative value of the compounds based on the induction periods and referredto We claim as our -invention: y

1. A method for stabilizing gasoline against deterioration thereof on storage which comprises adding to the gasoline a relatively small amount of an N-substituted aminophenol-in which one of the amino hydrogen atoms has been replaced hydrogen atoms has been replaced by an ethyl group and the other by a hydroxy alkyl group. 3. A method for stabilizing gasoline against deterioration thereof on storage which comprises of N-n-butyl N-beta hydroxy ethyl p-amino-. phenol.

gasoline against Y MgJlOO cc. copper dish Oxygen bomb stab. ind. Percent removed Emotive period, min. y-

inhibitor ratio- Water Caustic Orig Water Caustic Water Caustic washed washed a washed washed wash wash on alga-saline 37 218 100 st s5 N- -hydroxy-ethyl-N.-

butylp-aminophenol 1.38 3 7 13 295 170 110 6o 84 N b-hydroxy ethyl N octyl p-aminophenol 1.38 4 5 81 350 .235 43 1 9i The above data shows that particularly with 15 adding to the gasoline a relatively small amount of N-n-octyl-N-beta-hydroxy ethyl p-aminophenol.

5. Motor fuel com prising gasoline normally tending to deteriorate'on storage'and containing a relatively small amount of a N-substituted a relativelysmall amount of an ami'nophenol in which one of the amino hydrogen atoms has been replaced by an ethyl groupand the other by a hydroxy alkyl group. v

7. Motor fuel comprising gasoline normally tending to deteriorateon'storage and containing a relatively small amount of N-n-butyl-N-betahydroxy ethyl p-aminophenol. A

8. Motor fuel comprising gasoline normally tending to deteriorate on storage and containing a relatively small amountof N-n-octyl-N- beta-hydroxy ethyl p-aminophenol.

GUSTAV new. cnmrns a, Dayna. 

